Materials Research. 2014; 17(Suppl.

1): 3-8 © 2014

DDOI: http://dx.doi.org/10.1590/S1516-14392014005000057

Effects of Acid Treatment on the Clay Palygorskite: XRD, Surface Area,

Morphological and Chemical Composition

Katiane Cruz Magalhães Xaviera, Maria do Socorro Ferreira dos Santosb, Maria Rita Morais Chaves Santosa,

Marilia Evelyn Rodrigues Oliveiraa, Maria Wilma Nunes Cordeiro Carvalhoc,

Josy Antevelli Osajimaa, Edson Cavalcanti da Silva Filhoa*

Interdisciplinary Laboratory of Advanced Materials, Natural Science Center,

a

Federal University of Piauí – UFPI, CEP 64049-550, Teresina, PI, Brazil

b
Technology Center, Federal University of Piauí – UFPI, CEP 64049-550, Teresina, PI, Brazil
c
Chemical Engineering Department, Federal University of Campina Grande – UFCG,
CEP 58429-900, Campina Grande, PB, Brazil

Received: June 18, 2013; Revised: March 18, 2014

The palygorskite is an aluminum-magnesium silicate that has a fibrous morphology. Their physico-
chemical characteristics are the result of high surface area, porosity and thermal resistance which make
it an attractive adsorbent. Its adsorption capacity can be increased through chemical reactions and/or
heat treatments. The objective of this work is to verify the effects of acid activation on the palygorskite,
treated with HCl at 90 °C at concentrations of 2, 4 and 6 mol L–1 in 2 and 4 hours, with clay/acid
solution ratio 1 g 10 mL–1 and characterized by techniques: XRF, XRD and surface area. A significant
increase in specific surface area was observed in the sample treated with HCl at the concentration
6 mol L–1. The changes were more pronounced at stricter concentrations of acidity, with decreasing
intensity of reflection of the clay indicated in the XRD. These changes were confirmed in the XRF
with the leaching of some oxides and with increasing concentration of SiO2.

Keywords: Palygorskite clay, acid-activation, characterization.

1. Introduction
Palygorskite is a crystalline hydrated magnesium
aluminium silicate that exists in nature as a fibrous mineral
with large surface area, excellent chemical stability and
strong adsorption properties. It consists of two layers of
tetrahedral silica linked by magnesium ions in an octahedral
configuration, connected by a continuous plane of tetrahedral
basal oxygen atoms1. The tetrahedral basal oxygen atoms
invert apical direction at regular intervals coordinating talc
like ribbons. Each talc-like ribbon alternates with channels
along the fiber axis2.
The palygorskite has the theoretical formula: Si8Mg5O20
(OH)2 (OH2)4.4H2O, which was first proposed by Bradley3-5.
However, the chemical composition of these mineral
clays varies within certain limits according to their
origin. Considerable amounts of Al+3 can replace Mg+2
in the octahedral sheet. Thus, depending on the degree
of isomorphous substitution, the ideal palygorskite rich
in magnesium or aluminum would be: Si8(Mg5-3xAl2x)
O20(OH)2(OH2)4.4H2O, whose structure contains three
forms of water in its structure: zeolitic water, coordinated
and structural water6.
In addition to aluminum, other cations may replace
magnesium, albeit of a less extensive form. The presence of
trivalent cations into octahedral positions creates an excess
*e-mail: edsonfilho@ufpi.edu.br
of positive charge which is compensated by empty spaces
caused by two trivalent ions, whose chemical composition of
the palygorskite varies according to the origin of the sample7.
The differences in the ratio of divalent/trivalent cation,
which alter the chemical composition of the palygorskite,
will affect the proportion of trivalent ions located at the ends
and within the octahedral sheet, and carry the differences
in its behavior and composition, particularly in response to
acid leaching8.
Appropriate acid treatments of clay minerals modify
their surface area and/or the number of acid sites by
disaggregation of clay particles, elimination of mineral
impurities, removal of metal-exchange cations and proton
exchange. For palygorskite, acid activation can eliminate
impurities, change its composition, generate more active
OH– groups on its surface, increase its area and pore volume
as well as the number of adsorption sites by disaggregation
of palygorskite paticles9-11. Thus, acid treatment have been
used for increasing the surface area of clay minerals and for
obtaining from these minerals solids with a high numbers
of acid centers, properties that influence the application of
these materials in descolourization, adsorption and catalysis
in reactions in which catalysis with acidic properties are
requerid10.
The objective of this research is to analyze the structural
changes developed in the palygorskite after treatment by
4 Xavier et al.
hydrochloric acid at three different concentrations with
variations in time and with temperature of 90 °C through
the use of the techniques: XRF, XRD and specific surface
area (BET).
2. Experimental
2.1. Materials
It was used a sample of Palygorskite, from Guadalupe,
PI, provided in the form of agglomerate by the Itaoeste
company, which has a cation exchange capacity (CEC) of
40 meq/100g, and with structural formula: (Si8.05)(Mg1.59A
l1.74Fe0,32Ti0.084Mn0.023)(K0.052)O20(OH)2(OH2)4.nH2O[3]. The
natural clay dried at 25°, and ground was sieved entirely
on 200 mesh sieve. The hydrochloric acid (HCl) 35% PA
(VETEC) and distilled water was utilized in this work.
2.2. Acid activation
For the activation assays, it was treated, under magnetic
stirring, an amount of palygorskite in hydrochloric acid at
concentrations of 2, 4, 6 mol L–1 at 90 °C with reaction times
of 2 or 4 hours9-11. The mixture was stirred in a becker with
a cover in order in order to maintain the constant volume
of solution used, with the mass ratio of the clay/solution
volume, 1 g : 10 mL. Initially, aqueous solution was
prepared in the requerid concentration with hydrochloric
acid, which was added to the sample (10 g) and crushed,
which was contained in a glass container. After completion
of the reaction, the mixtures obtained were vacuum filtered
(Buchner funnel and conical flask), and washed with distilled
water until the pH of the filtrates remained at around 7. The
materials obtained were dried in an oven at 60 ± 5 °C and
after 24 hours were disaggregated in a mortar. The activated
samples were characterized by X-ray fluorescence, X-ray
diffraction and surface area.
2.3. Characterization of the palygorskite
The XRF analysis was performed on spectrometer for
X-ray fluorescence - (WDS) model BOL - FRX - 030. The
sample was prepared by fusion at a dilution of 1/10 and used
as a flux, a mixture of lithium borate (Li2B4O7 - LiBO2). The
X-Ray Diffraction (XRD) was performed on equipment
LabX - XRD 600, Shimadzu, with Cu-Kα radiation
(λ = 1.5406 Å) with 2θ in the range of 5° to 75°, with scan
rate of 2°/min and total exposure time of 40 minutes. The
surface area was determined in an apparatus for physical
adsorption of nitrogen Quantachrome NOVA 4200, using
BET method for processing the data. Secondary electron
images were acquired with a JEOL JSM 6360LV scanning
electron microscope, operating at 20 kV.
3. Results and Discussion
3.1. X-ray diffraction
The diffractograms of the natural clay and acid treated
are shown in Figure 1, of which the main indication of the
presence of palygorskite occurs by the appearance of peak at
8.5° (1.05 nm). Besides this, other peaks at 14.0° (0.62 nm)
and 28.1° (0.32 nm) are also observed in the sample of the
Materials Research
natural. Besides the palygorskite there is also the presence
of quartz, evidenced by the peak around 26.6° (0.34 nm).
Table 1 shows a comparison between data palygorskite used
in this work and data from crystallographic card (JCPDS-
ICCD 00-031-0783) of Clay, revealing that there are no
differences between them.
The intensity of the peaks characteristic at 8.5°
(1.051 nm), 14.0° (0.636 nm) and 28.1° (0.32 nm) decreased
progressively in intensity with increasing acid concentration
in the experimental conditions established, but does
not disappear. This is explained because when the acid
concentration is increased to treat a decrease in intensity of
the characteristic peak of palygorskite (8.5°), a fact caused
by the change of the crystalline structure and followed by
leaching in octahedral and tetrahedral sheets3,12,13.
The basal distances of the activated samples are
approximately equal to the natural sample; however
there are small displacements, as for example in the HCl
sample - 4 mol L–1/4H/90 °C, which occurs a displacement
of 1.03 to 1.00 nm.
In the activated samples under more intense conditions
of temperature of 90 °C and a time of 4 hours it is observed
that the peaks of palygorskite become broader, indicating
the loss of crystallinity. At the same time, it was observed
through the diffractograms, an increase in insoluble
impurities in the sample, and the main reflections correspond
to quartz which were found and become more intense
with increasing acid attack, progressing in both sets of
samples, indicating that the acid attack occurs only on the
palygorskite, with the decrease in the intensity peaks relating
to clay, with a consequent decrease in crystallinity, the only
observations verified14.
Figure 1. Diffractogram of natural palygorskite and activated
with HCl.
Table 1. Comparison of crystallographic planes of parlygorkite.
Peaks Crystallographic Card Palygorskite (This work)
8.5 1.04 nm 1.05 nm
14.0 0.63 nm 0.62 nm
28.1 0.31 nm 0.32 nm
26.6 0.34 nm 0.34 nm
2014; 17(Suppl. 1) Effects of Acid Treatment on the Clay Palygorskite: XRD, Surface Area, Morphological and Chemical Composition 5

3.2. XRF analysis
The results of XRF are shown in Table 2, which
shows the chemical compositions of natural and activated
palygorskites, where it is observed that Al2O3, Fe2O3, MgO,
and K2O are the major constituents of the octahedral sheets
of the clay.
The palygorskite is a magnesium silicate, which can
be substituted for aluminum in the structure. The natural
Figure 2. Measurements of surface area of the samples of
palygorskite natural and activated.
sample has 11.48% aluminum and 8.28% Mg. This indicates
that the substitution of magnesium by aluminum is larger10.
The amounts of Mg, Al and Fe were reduced with
increasing acid concentration, confirming that the ions
Mg2+, Al3+ and Fe3+ were leached in all activated samples.
After acid treatment for a long period of time (96 h and
50°C), the hydrochloric acid solution can convert part of the
crystals of palygorskite into amorphous silica15. However,
in this study this result was not observed, it is observed the
distinction between the plans and the similarity with the
initial crystalline sample, as observed in Figure 1, unlike a
diffraction pattern of an amorphous material, which appears
only a very broad peak.
Some explanations can be found in studies which
affirm that magnesium rich clays are more easily attacked
by acids and the octahedral sheets easily undergo leaching,
this because its fibers have a smaller size and thus offers a
greater specific surface area and a greater number of corners
and edges, points which are more easily attacked by acid.
However, samples rich in aluminum, as is the case with
clay of this research, have greater fiber length, as well as a
larger incidence of trivalent cations that limit the progress
of the attack6,15-18 Another explanation is found in researches
that consider that the Al occupies the center and the Mg,
exclusively, the edges of the octahedral ribbons of the
palygorskite which facilitates the leaching of the cations4,19.
When the palygorskite was treated in the condition
HCl - 6 mol L–1/2 h/90 °C, 53% of the A12O3, 70% Fe2O3 and

Table 2. Chemical Composition of the clays natural and activated with hydrochloridic acid, under different conditions.
Treatment MgO Al2O3 SiO2 K2O TiO2 MnO Fe2O3 Loss on Fire
Natural 8.28 11.48 63.67 0.32 0.87 0.21 3.27 11.90
2 mol L–1/2H/90°C 8.17 11.26 63.93 0.27 1.03 0.17 3.25 11.92
4 mol L–1/2H/90°C 5.01 7.26 71.09 0.11 0.89 ND 1.66 13.98
6 mol L–1/2H/90°C 3.29 5.42 78.97 0.18 0.90 ND 0.98 10.26
2 mol L–1/4H/90°C 5.72 8.09 72.10 0.14 1.11 ND 2.04 10.80
4 mol L–1/4H/90°C 5.00 7.61 73.84 0.14 0.93 0.04 1.80 10.64
6 mol L–1/4H/90°C 4.79 6.97 75.65 0.15 0.97 ND 1.71 9.76
ND = Non-detectable.

Figure 3. SEM micrographs of natural palygorskite.

6 Xavier et al. Materials Research

Figure 4. SEM micrographs of samples of activated palygorskites with HCl at 90 °C.

2014; 17(Suppl. 1) Effects of Acid Treatment on the Clay Palygorskite: XRD, Surface Area, Morphological and Chemical Composition
57% of MgO were removed from the sample of palygorskite.
In this sample was found 78.97% SiO2. The percentage of
the content of SiO2 increases with the exiting of Mg, Al, Fe
and others, besides silicon being the dominant constituent
in the tetrahedral sheets and being relatively resistant to
acid attack3,20.
3.3. Surface area
The surface area measurements of natural and activated
palygorskite are shown in Figure 2, showing the increased
value of the area as the acid treatment progresses. The natural
palygorskite has a surface of 113 m2 g–1. The maximum is
310 m2 g–1 in the sample 6M/2H/90 °C. The surface area of
the sample treated at 6M/4H/90 °C decreases slightly to a
value of 290 m2 g–1, as shown in Figure 2, it being possible
when the treatment time was 2 hours, but there was variation
in the surface area when the material was treated in a high
concentration (6 mol L–1). And treatments using time of
4 hours is observed that as the concentration increases,
there is also an increase in surface area due to the strength
of the acid.
The increased surface area of the natural palygorskite to
acid treated samples is related mainly to the elimination of
exchangeable cations and increase of SiO2. The increased
surface area to a maximum value and additional decrease
were described in the literature for activation with acid on
the palygorskite21,22 and clays such as: halloysites23 , and
bentonites24.
The surface area is one of the most important
physicochemical properties of palygorskite, especially
when it is used as an adsorbent to remove heavy metals and
dyes ions. The specific surface area of the acid activated
palygorskite has great influence on the adsorption of Cu (II)2.
3.4. Morphological analysis
In order to check the morphology of natural and
activated samples with hydrochloric acid are shown in
Figures 3 and 4.
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4. Conclusions
The progressive destruction of the structures of
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concentration. This partial degradation of the structure
of the mineral clay under study is due to leaching in the
octahedral layer. The acid treatment did not affect severely
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All techniques used showed that the more intense the acid
attack, the greater the leaching of the octahedral cations,
causing chemical and structural changes in the palygorskite,
being observed a significant increase in surface area of the
solid obtained.
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